Late transition metal complexes, their use as catalysts and polymers therefrom

ABSTRACT

The invention provides a novel metal complex which, when used with an activating cocatalyst, provides a novel catalyst composition. The invention also provides a polymerization method which utilizes the catalyst composition to produce polymers and copolymers containing polar monomer groups. More specifically, the invention comprises a composition comprising the formula LMXZ n  wherein X is selected from the group consisting of halides, hydride, triflate, acetates, borates, C 1  through C 12  alkyl, C 1  through C 12  alkoxy, C 3  through C 12  cycloalkyl, C 3  through C 12  cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, and any other moiety into which a monomer can insert. M is selected from the group consisting of Cu, Ag, and Au. L is a nitrogen-containing bidentate ligand having more than two nitrogen atoms. Z is a neutral coordinating ligand and n equals 0, 1, or 2.

FIELD OF THE INVENTION

[0001] The invention is directed towards a late transition metalpolymerization catalyst complex and its use in forming polymers fromolefins or polar monomers and copolymers from olefins and polarmonomers.

BACKGROUND

[0002] Polymers and copolymers may be formed from olefinic monomers byusing transition metal catalyst technology. Ziegler-Natta catalysts havebeen used for many years while in more recent years metallocenecatalysts have been preferred in certain applications since thepolyolefins produced via metallocene catalysis often possess superiorproperties. The most well-known metallocene technology employs catalystscontaining early transition metal atoms such as Ti and Zr.

[0003] Even though polyolefins formed by such metallocene catalystspossess certain enhanced properties over polyolefins produced byconventional Ziegler-Natta catalysts, further improvements in propertiessuch as wettability and adhesiveness may be possible. It is believedthat including polar monomers in an olefinic polymer or copolymer wouldimprove these, and possibly other, properties. Unfortunately, polarmonomers tend to poison early transition metal catalysts.

[0004] Certain late transition metal complexes such as those containingpalladium and nickel, are more forgiving when incorporating certainpolar monomers. However, most of these catalyst compositions are costlyand produce highly branched polymers (e.g., 85-150 branches/1000 carbonatoms). Also, the functionalities are not in the chain but at the endsof branches. Consequently, they are limited to polar monomer contents toabout 15 mol % or less. Another disadvantage of these compositions isthat they incorporate only a limited number of polar monomers such asalkyl acrylates and vinyl ketones.

[0005] Recently, novel late transition organometallic catalysts havebeen made to address the aforementioned problems. More specifically,U.S. Pat. No. 6,037,297 to Stibrany et al., herein incorporated byreference, details group 11 metal (Cu, Ag and Au) containing catalystcompositions having a pseudotetrahedral geometry that are useful informing polymers and copolymers having hydrocarbyl polar functionality.

[0006] However, there is still a need to explore other group 11 metalcomplexes for use in polymerization processes. Ideally, these latetransition metal complexes should be capable of forming olefinicpolymers and copolymers containing polar monomers which are not highlybranched, have polymer chain functionality and are capable ofincorporating a wider variety of polar monomers.

SUMMARY

[0007] The instant invention provides a late transition metal complexwhich can be used with an activating cocatalyst to produce polymers andcopolymers. Also, like the invention described in U.S. Pat. No.6,037,297, the instant invention can be used to produce polymers andcopolymers containing polar monomers.

[0008] In one embodiment, the invention is a composition having theformula LMXZ_(n) wherein X is selected from the group consisting ofhalides, hydride, triflate, acetates, borates, C₁ through C₁₂ alkyl, C₁through C₁₂ alkoxy, C₃ through C₁₂ cycloalkyl, C₃ through C₁₂cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, and anyother moiety into which a monomer can insert. M is selected from thegroup consisting of Cu, Ag, and Au. L is a nitrogen-containing bidentateligand with more than two nitrogen atoms. Z is a neutral coordinatingligand and n equals 0, 1, or 2.

[0009] In another embodiment, the invention is a catalyst compositioncomprising the reaction product of: a metal complex having the formulaLMXZ_(n), as described above, and an activating cocatalyst. Thisembodiment of the invention is particularly useful in polymerizationchemistry.

[0010] In yet another embodiment, the invention provides a method forusing the composition to produce polymers and copolymers which containpolar monomer units. The method includes contacting the monomers underpolymerization conditions with a catalyst composition comprising acomposition having the formula LMXZ_(n), as defined above, and anactivating cocatalyst. Optionally, an oxidizing agent may also beemployed during this process.

[0011] These and other features, aspects and advantages of the presentinvention will become better understood with regard to the followingdescription and appended claims.

DESCRIPTION

[0012] The invention relates to a novel metal complex which, when usedwith an activating cocatalyst, provides a novel catalyst composition.The invention also provides a polymerization method which utilizes thecatalyst composition. Generally speaking, the method of the inventionproduces polymers and copolymers containing polar monomer groups.

[0013] In one embodiment, the invention comprises a compositioncomprising the formula LMXZ_(n) wherein X is selected from the groupconsisting of halides, hydride, triflate, acetates, borates, C₁ throughC₁₂ alkyl, C₁ through C₁₂ alkoxy, C₃ through C₁₂ cycloalkyl, C₃ throughC₁₂ cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, andany other moiety into which a monomer can insert; M is selected from thegroup consisting of Cu, Ag, and Au; L is a nitrogen-containing bidentateligand with more than two nitrogen atoms; Z is a neutral coordinatingligand; wherein n equals 0, 1, or 2.

[0014] The geometric configuration of the metal complex of the instantinvention can be either pseudotetrahedral or trigonal planar dependingon the value of n (i.e., n can equal 0, 1 or 2). It should beappreciated by those skilled in the art that although the term“pseudotetrahedral” is used to describe the geometric structure of themetal complex, it does not exclude a pure “tetrahedral” geometricalarrangement. The prefix “pseudo” is used throughout the specification tomost accurately describe the non-limiting embodiments described herein.Similarly, the term “trigonal planar” should be understood by thoseskilled in the art to also include geometric configurations which areapproximately trigonal planar.

[0015] When the metal composition is reacted with an activatingcocatalyst such as methyl alumoxane (a.k.a., “MAO”) a catalystcomposition is created. Thus, in another embodiment, the invention is acatalyst composition comprising the reaction product of: (a) A metalcomplex having the formula LMXZ_(n) wherein X is selected from the groupconsisting of halides, hydride, triflate, acetates, borates, C₁ throughC₁₂ alkyl, C₁ through C₁₂ alkoxy, C₃ through C₁₂ cycloalkyl, C₃ throughC₁₂ cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, andany other moiety into which a monomer can insert; M is selected from thegroup consisting of Cu, Ag, and Au; L is a nitrogen-containing bidentateligand with more than two nitrogen atoms; Z is a neutral coordinatingligand; where n equals 0, 1, or 2; and (b) an activating cocatalyst.

[0016] Furthermore, by controlling the temperature, catalyst loading,ligand structure, and residence time, product selectivity can beadjusted to produce individual polymers and copolymers with highselectivity. Hence, in yet another embodiment, the invention provides amethod for producing polymers and copolymers.

[0017] Ideally, Z is weakly coordinating and sufficiently labile toallow activation of the catalyst. In a preferred embodiment composition,for each occurrence of Z, each Z is independently selected from thegroup consisting of diethylether, tetrahydrofuran, acetonitrile,benzonitrile, dioxane, acetone, 2-butanone, phenylisocyanate, ethylene,carbon monoxide, 1-hexene, and norbornene.

[0018] In another preferred embodiment of this invention is a complexhaving the formula LMXZ_(n), as described above, where L is anitrogen-containing bidentate ligand represented by the formula:

[ARA′] and [AA′],

[0019] wherein A and A′ are independently selected from the groupconsisting of

[0020] wherein R1 is independently selected from the group consisting ofhydrogen, C₁ through C₁₂ straight chain or branched alkyl, C₃ throughC₁₂ cycloalkyl, aryl, and trifluoroethane;

[0021] R2 and R3 are independently selected from the group consisting ofhydrogen, C₁ through C₁₂ straight chain or branched alkyl, C₃ throughC₁₂ cycloalkyl, C₁ through C₁₂ alkoxy, F, Cl, SO₃, C₁ through C₁₂perfluoroalkyl, and N(CH₃)₂;

[0022] R is selected from the group consisting of non-substituted C₁through C₁₂ alkyl, C₃ through C₁₂ cycloalkyl; methoxy; amino; halo; C₁through C₁₂ haloalkyl substituted alkyl; cycloalkyl of up to 12 carbonatoms, C₁-C₄₀ aryl; and C₁-C₄₀ alkylaryl.

[0023] X is selected from the group consisting of halogens, hydride,triflate, acetate, trifluoroacetate, perfluorotetraphenylborate,tetrafluoroborate, C₁ through C₁₂ alkyl, C₁ through C₁₂ alkoxy, C₃through C₁₂ cycloalkyl, C₃ through C₁₂ cycloalkoxy, aryl, and any othermoiety into which a monomer can insert such as an atom, or group ofatoms, covalently or inonically bonded to M; Z is a neutral coordinatingligand; where n equals 0, 1, or 2. In a preferred embodiment, for eachoccurrence of Z, each Z is independently selected from the groupconsisting of diethylether, tetrahydrofuran, acetonitrile, benzonitrile,dioxane, acetone, 2-butanone, phenylisocyanate, ethylene, carbonmonoxide, 1-hexene, and norbornene.

[0024] Accordingly, some of the ligands of the present invention havethe following structures:

[0025] For compactness, some bonds are shown without termination; thesebonds are terminated by methyl groups.

[0026] Cu is preferred for M. Among the options for X, halogens arepreferred. Suitable non-halide options for X include, but are notlimited to, triflate, trifluoroacetate, perfluorotetraphenyl borate, ortetrafluoro borate, hydride, alkyl groups or any other ligand into whicha monomer can insert such as an atom, or group of atoms, covalently orinonically bonded to M.

[0027] Among the metal complexes of the present invention, particularlypreferred embodiments are those having the2,2′bis[2-(1-alkylbenzimidazol-2yl)]biphenyl, where the alkyl group isfrom C₁-C₂₀, and for X is chloride.

[0028] Generally, the 2,2′bis[2-(1-alkylbenzimidazol-2yl)]biphenylligands having copper as the metal and chlorine as X, and C₁-C₂₀ as R₁,have the structure

[0029] Preferred embodiments of specific metal complexes include, butare not limited to, the following:

[0030][(2,2′-bis[2-(1-ethylbenzimidazol-2yl)]biphenyl)(acetonitrile)copper(I)](tetrafluoroborate)

[0031] , and(2,2′-bis[2-(1-ethylbenzimidazol-2yl)]biphenyl)copper(I)chloride

[0032] Advantageously, the catalysts of the present invention are notpoisoned by compounds containing hydrocarbyl polar functional groupswhen used in the formation of polymers and copolymers synthesized all orin part from olefinic monomers. As such, the catalysts of the presentinvention are useful in preparing polymers and copolymers formed fromolefinic monomers, such as polyethylene; polymers and copolymers formedfrom monomers containing hydrocarbyl polar functional groups such aspoly(methyl methacrylate); and copolymers derived from olefins andmonomers containing hydrocarbyl polar functional groups such as poly(ethylene-co-methyl methacrylate).

[0033] The activating cocatalysts used in conjunction with the metalcomplex defined above include, but are not limited to, aluminumcompounds containing an Al—O bond such as the alkylalumoxanes such asmethylalumoxane (“MAO”), isobutyl modified methylalumoxane (“MMAO”);“dry” [i.e., sovent free and Me₃Al (“TMA”) free] MAO; aluminum alkyls;aluminum halides; alkylaluminum halides; Lewis acids other than any ofthe foregoing list; and mixtures of the foregoing can also be used inconjunction with alkylating agents, such as methyl magnesium chlorideand methyl lithium. Examples of such Lewis acids are those compoundscorresponding to the formula: R″″₃B, or R₃″″Al wherein R″″ independentlyeach occurrence is selected from hydrogen, silyl, hydrocarbyl,halohydrocarbyl, alkoxide, aryloxide, amide or combinations thereof,said R″″ having up to 30 nonhydrogen atoms.

[0034] It is to be appreciated by those skilled in the art, that theabove formula for the preferred Lewis acids represents an empiricalformula, and that many Lewis acids exist as dimers or higher oligomersin solution or in the solid state. Other Lewis acids which are useful inthe catalyst compositions of this invention will be apparent to thoseskilled in the art.

[0035] Other examples of such cocatalysts include salts of group 13element complexes. These and other examples of suitable cocatalysts andtheir use in organometallic polymerization are discussed in U.S. Pat.No. 5,198,401 and PCT patent documents PCT/US97/10418 andPCT/US96/09764, all incorporated by reference herein.

[0036] Preferred activating cocatalysts include trimethylaluminum,triisobutylaluminum, methylalumoxane, alkyl modified alumoxanes, “dry”alumoxanes, chlorodiethyaluminum, dichloroethylaluminum, triethylboron,trimethylboron, triphenylboron and halogenated, especially fluorinated,triaryl boron and aluminum compounds, carboranes and halogenatedcarboranes.

[0037] Most highly preferred activating cocatalysts includetriethylaluminum, methylalumoxane, and fluoro-substituted aryl boranesand borates such as tris(4-fluorophenyl)boron,tris(2,4-difluorophenylboron), tris(3,5-bis(trifluoromethylphenyl)boron, tris(pentafluorophenyl) boron, pentafluorophenyl-diphenyl boron,and bis(pentafluorophenyl) phenylboron and tetrakis (pentafluorophenyl)borate. Such fluoro-substituted arylboranes may be readily synthesizedaccording to techniques such as those disclosed in Marks, et al., J. Am.Chem. Soc., 113, 3623-3625 (1991). Fluorinated tetraaryl borates oraluminates and perfluoro tetranapthyl borates or aluminates, are alsowell known in the art.

[0038] The catalyst can be utilized by forming the metal complexLMXZ_(n), as defined above, and where required combining the activatingcocatalyst with the same in a diluent. Optionally, an oxidizing agentmay also be utilized in conjunction with the cocatalyst. Oxidizingagents may include, but are not limited to: NOBF₄; 1,4-benzoquinone;tetrachloro-1,4-benzoquinone; AgClO₄; Ag(C₆F₅)₄B; ferricinium (C₆F₅)₄B;(3, 5(CF₃)₂(C₆H₄)B)Cp₂Fe⁺; and (3, 5(CF₃)₂(C6H₄)B)Cp₂*Fe⁺. Thepreparation may be conducted in the presence of one or more additionpolymerizable monomers, if desired. Preferably, the catalysts areprepared at a temperature within the range from −100° C. to 300° C.,preferably 0° C. to 250° C., most preferably 0° C. to 100° C. Suitablesolvents include liquid or supercritical gases such as CO₂, straight andbranched-chain hydrocarbons such as isobutane, butane, pentane, hexane,heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbonssuch as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, halogenated hydrocarbons such as chlorobenzene, anddichlorobenzene perfluorinated C₄₋₁₀ alkanes and aromatic andalkyl-substituted aromatic compounds such as benzene, toluene andxylene. Suitable solvents also include liquid olefins which may act asmonomers or comonomers including ethylene, propylene, butadiene,1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene,and 4-vinycylohexane, (including all isomers alone or in mixtures).Other solvents include anisole, methylchloride, methylene chloride,2-pyrrolidone and N-methylpyrrolidone. Preferred solvents are aliphatichydrocarbons and aromatic hydrocarbon, such as toluene.

[0039] When an activating cocatalyst is used to form the catalystcomposition, the equivalent ratio of metal complex to activatingcocatalyst is preferably in a range from 1:0.5 to 1:10⁴, more preferablyfrom 1:0.75 to 1:10³. In most polymerization reactions the equivalentratio of catalyst:polymerizable compound employed is from 10⁻¹²: to10⁻¹:1, more preferably from 10⁻⁹:1 to 10⁻⁴:1.

[0040] Olefinic monomers useful in the forming homopolymers andcopolymers with the catalyst of the invention include, but are notlimited to, ethylenically unsaturated monomers, nonconjugated dienes,and oligomers, and higher molecular weight, vinyl-terminated macromers.Examples include C₂₋₂₀ olefins, vinylcyclohexane, tetrafluoroethylene,and mixtures thereof. Preferred monomers include the C₂₋₁₀ α-olefinsespecially ethylene, propylene, isobutylene, 1-butene, 1-hexene,4-methyl-1-pentene, and 1-octene or mixtures of the same.

[0041] Monomers having hydrocarbyl polar functional groups useful informing homo and copolymers with the catalyst of the invention, arevinyl ether and C₁ to C₂₀ alkyl vinyl ethers such as n-butyl vinylether, acrylates, such as C₁ to C₂₄, or alkyl acrylates such as t-butylacrylate, and lauryl acrylate, as well as methacrylates such as methylmethacrylate.

[0042] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from −100° C. to 250° C.preferably 0° C. to 250° C., and pressures from atmospheric to 2000atmospheres (200 Mpa). Suitable polymerization conditions include thoseknown to be useful for metallocene catalyst when activated by aluminumor boron-activated compounds. Suspension, solution, slurry, gas phase orother process condition may be employed if desired. The catalyst may besupported and such supported catalyst may be employed in thepolymerizations of this invention. Preferred supports include alumina,silica, polymeric supports and meso-porous materials.

[0043] The polymerization typically will be conducted in the presence ofa solvent. Suitable solvents include those previously described asuseful in the preparation of the catalyst. Indeed, the polymerizationmay be conducted in the same solvent used in preparing the catalyst.Optionally, of course, the catalyst may be separately prepared in onesolvent and used in another.

[0044] The polymerization will be conducted for a time sufficient toform the polymer and the polymer is recovered by techniques well knownin the art and illustrated in the following non-limiting examples whichhelp to further described the invention.

EXAMPLE 1 Preparation of [Cu(diEtBBIL)(ACN)](BF₄)

[0045] In an argon glovebox a colorless solution of 35 mg (0.11 mmol) ofCu(ACN)₄(BF₄) in 8 mL of acetonitrile was prepared. Then, 50 mg (0.11mmol) of diEtBBIL was added to the solution and thoroughly mixed. Theflask containing the colorless solution was then placed in a sealed jarcontaining diethylether to allow vapor diffusion. After one daycolorless crystals ofrac-[(2,2′-bis[2-(1-ethylbenzimidazol-2yl)]biphenyl)(acetonitrile)copper(I)](tetrafluoroborate)were obtained. ¹H NMR (CDCl₃): δ=7.65(d, J=6,7 Hz, 2H), 7.54(dd, J=7.8Hz, J=17.9 Hz, 4H), 7.33(m, 8H), 6.93(d, J=7,4 Hz, 2H), 4.47(dm, J=40.3Hz, 4H), 2.15(s, 3H), 1.66(t, J=6.8 Hz, 6H). X-ray crystallogrphic data:monoclinic, P2(1), Z=4, a=16.952(3), b=15.527(3), c=12.946(2), α=90,β=111.33(3), γ=90, V=3174.15.

EXAMPLE 2 Preparation of Cu(I)(diEtBBIL)Cl by reduction

[0046] A 100 mg quantity of 10μ copper powder was placed in a 100 mLround bottom flask with a side arm. Then, 2 mL of triethylorthoformateand 20 mL of acetonitrile were added to the flask. The flask was fittedwith bubbler and was degassed under a continuous flow of nitrogen. Then,33 mg (0.19 mmol) of CuCl₂.2 H₂O was added to the stirring mixture undera positive flow of nitrogen to give a green solution. Then, 170 mg (0.38mmol) of diEtBBIL was added to the flask to give a yellow solution. Themixture was stirred under nitrogen for more than 72 hours. The flaskcontaining the colorless solution and remaining solid was then filteredto give a colorless filtrate. The solvent was removed under a flow ofnitrogen to give a white solid. The solid was placed under high vacuuman additional hour to give 144 mg of white(2,2′-bis[2-(1-ethylbenzimidazol-2yl)]biphenyl)copper(I)chloride. ¹H NMR(CDCl₃): δ=8.08(m, 2H), 7.69(m, 1H), 7.53(m, 3H), 7.27(m, 6H), 6.95(dm,4H), 4.38(dm, 4H), 1.58(m, 3H), 1.90(m, 3H).

EXAMPLE 3 Preparation of Polyethylene Using [Cu(I)(diEtBBIL)(ACN)](BF₄)

[0047] A 32.1 mg (0.051 mmol) quantity of Cu(diEtBBIL)(MeCN))BF₄ wasweighed out in a glass liner under argon. Then, 30 mL of toluene wasadded to the liner, followed by 2.0 g of 30 wt. % MAO (0.010 mol)resulting in a pale yellow slurry. The liner was placed in a 300 mL Parrreactor which was sealed, pressurized with ethylene and heated to 80° C.The reaction was run for 15 hours at 720 psig. At the end of this timeperiod, the reactor was cooled, vented and quenched with 5 mL ofmethanol. Then the polymer was precipitated out in 150 mL of acidicmethanol (10%). The polymer was isolated by filtration and dried undervacuum at 50° C. for a day. Yield: 0.8 g. T_(m): 142° C. (second heat).¹³C NMR (ppm, 125° C. tetrachloroethane): 29.5 (s, —CH₂—CH₂—); noevidence of end groups and branch points up to the detection limits ofabout one carbon per 500-1000 carbons.

EXAMPLE 4 Preparation of Poly(t-butyl acrylate) Using[Cu(I)(diEtBBIL)(ACN)](BF₄)

[0048] A 32.1 mg (0.051 mmol) quantity of Cu(diEtBBIL)(MeCN))BF₄ wasadded to a 100 mL round-bottomed flask in an argon glovebox. 10 mL oftoluene was added to the flask, followed by 1.02 g of 30 wt. % MAO (5.3mmol) resulting in an yellow slurry. 5.9 g of t-butyl acrylate (freshlydistilled from CaCl₂ and stabilized with 300 ppm of phenathiazine) wasadded to the slurry. The slurry was allowed to stir at room temperaturefor 18 hours in the dark. At the end of this time period, the reactionwas quenched with 5 mL of methanol and then the polymer was precipitatedout in 150 mL of acidic methanol (10%). The polymer was isolated byfiltration and dried under vacuum at 40° C. for a day. Yield: 14%. ¹³CNMR (ppm, CDCl₃): 28.2 (s, —CH₂—CH(COOC(CH₃)₃)—), 34.3-37.6 (m,—CH₂—CH(COOC(CH₃)₃)—), 42-43.5 (m, —CH₂—CH(COOC(CH₃)₃)—), 80.5 (m,—CH₂—CH(COOC(CH₃)₃)—), 173.2-174.1 (m, —CH₂-CH(COOC(CH₃)₃)—), 39% rr,47% mr, 14% mm (by integration of methine peak).

EXAMPLE 5 Preparation of Polyethylene Using [Cu(I)(diEtBBIL)(ACN)](BF₄)

[0049] The polymerization was run using a mixture prepared by dissolving21.1 mg (0.033 mmol) of [Cu(diEtBBIL)(ACN)](BF₄) in 80 ml of toluene togive a colorless solution. This was followed by the addition of 100 mgof NOBF₄ (0.85 mmol) maintaining a colorless solution. This was followedby the addition of 1.5 ml of 30% MAO to give an intense yellow solution.The Parr reactor was pressurized with 550 psig of ethylene and heated to80° C. and maintained at 80° C. for 20.75 hours during which thepressure dropped from 560 psig to 540 psig. The polymerization mixturewas cooled and quenched with methanol to give 31 mg of solidpolyethylene upon workup.

EXAMPLE 6 Preparation of Poly(t-butyl acrylate-ethylene)

[0050] A 24.1 mg (0.045 mmol) quantity of Cu(diEtBBIL)Cl was weighed outin a glass liner under argon. 30 mL of toluene was added to the liner,followed by 1.98 g of 30 wt. % MAO (0.010 mol) resulting in a paleyellow slurry. Next, 10.7 grams of t-butyl acrylate (t-butyl acrylatewas distilled from CaCl₂, degassed and taken into the glove box, thenapproximately 100 ppm phenathiazine was added) was added to the slurry.The liner was placed in a 300 mL Parr reactor which was sealed,pressurized with ethylene and heated to 80° C. The reaction was run for17 hours at 840 psig. At the end of this time period, the reactor wascooled, vented and quenched with 5 mL of methanol and then the polymerwas precipitated out in 300 mL of acidic methanol (10%). The polymer wasisolated by filtration and dried under vacuum at 60° C. for a day. Theyield was 4.5 g. The polymer was extracted in THF in a soxhlet extractorto remove any catalyst residue and characterized.

[0051] The composition of the copolymers was determined by ¹³C-NMR inCDCl₃. The acrylate ester content was calculated by averaging theintegral values for the acrylate carbonyl and quarternary carbon oft-butyl group. Ethylene content is then obtained by correcting the totalaliphatic integral for the t-butyl acrylate integration. Furthermore,acrylate-centered traits were quantified by integration of threeclusters of methine resonances: EAE : 46.5, EAA/AAE: 44.2, AAA: 42.2ppm. The copolymer was found to have 76 mol % t-butyl acrylate withEAE:EAA/AAE:AAA=8:38:53.

[0052] The foregoing examples clearly demonstrate that the novelcomposition of the instant invention can be used as an effectivepolymerization catalyst to make polymers and copolymers includingcopolymers having polar functionality. More specifically, the examplesshow how polar monomers can be readily polymerized without poisoning thecatalyst. Also, the chain, as opposed to the branches, contain asignificant quantity of the polar monomer(s). Furthermore, the polymersformed are not highly branched. Additionally, the examples show that thepolymers formed have a high percent of polar monomer content (e.g.,greater than about 15 mol %). Finally, there are a variety of polarmonomers which may be incorporated into the olefinic polymer andcopolymer products. These features overcome the disadvantages of themost organometallic catalyst technology used today as discussed above inthe background section.

What is claimed is:
 1. A composition comprising the formula LMXZ_(n)wherein X is selected from the group consisting of halides, hydride,triflate, acetates, borates, C₁ through C₁₂ alkyl, C₁ through C₁₂alkoxy, C₃ through C₁₂ cycloalkyl, C₃ through C₁₂ cycloalkoxy, aryl,thiolates, carbon monoxide, cyanate, olefins, and any other moiety intowhich a monomer can insert; M is selected from the group consisting ofCu, Ag, and Au; L is a nitrogen-containing bidentate ligand with morethan two nitrogen atoms; Z is a neutral coordinating ligand; wherein nequals 0, 1, or
 2. 2. The composition according to claim 1 wherein foreach occurrence of Z, each Z is independently selected from the groupconsisting of diethylether, tetrahydrofuran, acetonitrile, benzonitrile,dioxane, acetone, 2-butanone, phenylisocyanate, ethylene, carbonmonoxide, 1-hexene, and norbornene.
 3. A catalyst composition comprisingthe reaction product of: (a) A metal complex having the formula LMXZ_(n)wherein X is selected from the group consisting of halides, hydride,triflate, acetates, borates, C₁ through C₁₂ alkyl, C₁ through C₁₂alkoxy, C₃ through C₁₂ cycloalkyl, C₃ through C₁₂ cycloalkoxy, aryl,thiolates, carbon monoxide, cyanate, olefins, and any other moiety intowhich a monomer can insert; M is selected from the group consisting ofCu, Ag, and Au; L is a nitrogen-containing bidentate ligand having morethan two nitrogen atoms; Z is a neutral coordinating ligand; wherein nequals 0, 1, or 2; and (b) an activating cocatalyst.
 4. The compositionaccording to claim 3 wherein M is Cu.
 5. The composition according toclaim 3 wherein for each occurrence of Z, each Z is independentlyselected from the group consisting of diethylether, tetrahydrofuran,acetonitrile, benzonitrile, dioxane, acetone, 2-butanone,phenylisocyanate, ethylene, carbon monoxide, 1-hexene, and norbornene.6. The composition according to claim 3 wherein the activatingcocatalyst is methyl alumoxane.
 7. The composition according to claim 3wherein X is hydride.
 8. The composition according to claim 3 wherein Xis triflate.
 9. A method for polymerizing olefinic monomers selectedfrom the group consisting of: (a) acyclic aliphatic olefins, (b) olefinshaving a hydrocarbyl polar functionality and (c) mixtures of (i) atleast one olefin having a hydrocarbyl polar functional group and (ii) atleast one acyclic aliphatic olefin, the method comprising contacting theolefinic monomers under polymerization conditions with a catalystcomposition comprising the reaction product of: (a) A metal complexhaving the formula LMXZ_(n) wherein X is selected from the groupconsisting of halides, hydride, triflate, acetates, borates, C₁ throughC₁₂ alkyl, C₁ through C₁₂ alkoxy, C₃ through C₁₂ cycloalkyl, C₃ throughC₁₂ cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, andany other moiety into which a monomer can insert; M is selected from thegroup consisting of Cu, Ag, and Au; L is a nitrogen-containing bidentateligand with more than two nitrogen atoms; Z is a neutral coordinatingligand; wherein n equals 0, 1, or 2; and (b) an activating cocatalyst.10. The method according to claim 9 further comprising contacting saidmetal complex with an oxidizing agent.
 11. The composition according toclaim 9 wherein M is Cu.
 12. The composition according to claim 9wherein for each occurrence of Z, each Z is independently selected fromthe group consisting of diethylether, tetrahydrofuran, acetonitrile,benzonitrile, dioxane, acetone, 2-butanone, phenylisocyanate, ethylene,carbon monoxide, 1-hexene, and norbornene.
 13. The composition accordingto claim 9 wherein the activating cocatalyst is methyl alumoxane. 14.The composition according to claim 9 wherein X is hydride.
 15. Thecomposition according to claim 9 wherein X is triflate.